JPH05155836A - N-phenyltetrahydrophthalamic acid derivative and herbicide containing the derivative as active component - Google Patents

Abstract

PURPOSE:To provide a new tetrahydrophthalamic acid derivative having excellent herbicidal activity and high safety and useful as a herbicide widely applicable to upland field, paddy field, orchard, pasture, lawn, forestry, non-plowed land, etc. CONSTITUTION:The N-phenyltetrahydrophthalamic acid derivative of formula I (X and Y are H or halogen; R<1> and R<2> are lower alkyl, lower alkenyl or lower alkynyl; R<2> may be alkali metal), e.g. N-(4'-chloro-2'-fluoro-5'- propargyloxyphenyl)-3,4,5,6-tetrahydrophthalamic acid methyl ester. The compound can be produced by (a) reacting a compound of formula II with an alkylating agent in the presence of a diluent or (b) reacting a compound of formula III (R<3> is H or halogen; R<4> is H or lower alkyl; Z is halogen) with a compound of formula IV (R<2> is lower alkenyl or lower alkynyl) and treating the reactional product with a protonic solvent or (c) treating a compound of formula II with an alkali metal hydroxide.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel compound N
It relates to a phenyltetrahydrophthalamic acid derivative and a herbicide containing the derivative as an active ingredient.
INDUSTRIAL APPLICABILITY The N-phenyltetrahydrophthalamic acid derivative of the present invention has excellent herbicidal activity and is useful as a herbicide that can be widely applied to fields, paddy fields, orchards, meadows, lawns, forests, non-agricultural fields, and the like. It is also highly safe for crops.

[0002]

2. Description of the Related Art The herbicidal activity of tetrahydrophthalamic acid derivatives has been well known in the past, and is disclosed in, for example, JP-A-48.
N- (4'-chlorophenyl) -3,4,5,6-tetrahydrophthalamic acid methyl ester disclosed in U.S. Pat.

[0003]

[Problems of the prior art] However, the conventional herbicidal activity of tetrahydrophthalamic acid derivatives is not always sufficient, or the herbicidal spectrum against weeds is greatly limited, and in addition, the selectivity between crops and weeds is insufficient. Without
There is a problem with crop safety.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, contains a novel compound having excellent herbicidal activity and high safety for crops, and an active ingredient containing the same. The purpose is to provide a herbicide that

[0005]

The present inventors have found that a novel N-phenyltetrahydrophthalamic acid derivative having a specific substituent has extremely excellent herbicidal activity, selectivity and herbicidal spectrum. Completed the invention.

That is, the present invention has the general formula [I]

[0007]

[Chemical 3]

(Wherein, X and Y independently represent a hydrogen atom or a halogen atom, R ¹ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group, and R ² represents a lower alkyl group, a lower alkenyl group or a lower group. An N-phenyltetrahydrophthalamic acid derivative represented by alkynyl group or alkali metal) and a herbicide containing the derivative as an active ingredient.

The compound [I] of the present invention can be synthesized, for example, by the following method. [Synthesis Method a] General formula [II] when R ² is a lower alkyl group in general formula [I]

[0010]

[Chemical 4]

(Wherein X and Y each independently represent a hydrogen atom or a halogen atom, and R ¹ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group) and a compound such as an ether is used as a diluent. It is obtained by reacting with an alkylating agent such as diazoalkane or dialkylsulfate in the presence.

The phthalamic acid of the general formula [II] as a starting material can be synthesized by a general synthetic method with reference to JP-A-59-67255. [Synthesis Method b] In the general formula [I], R ² is a lower alkenyl group or a low alkenyl group.
In the case of secondary alkynyl groups, general formula [III]

[0013]

[Chemical 5]

(Wherein X and Y independently represent a hydrogen atom or a halogen atom, R ¹ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group, R ³ represents a hydrogen atom or a halogen atom, and R 3 ⁴ represents a hydrogen atom or a lower alkyl group, and Z represents a halogen atom), and a compound represented by the general formula [IV]

[0015]

[Chemical 6]

(Wherein R ² represents a lower alkenyl group or a lower alkynyl group) in the presence of an organic base such as triethylamine or an inorganic base such as potassium hydroxide, benzene, toluene, N, It can be obtained by treating the product obtained by the reaction in an inert solvent such as N-dimethylformamide with a protic solvent such as water or methanol.

[Synthesis Method c] When R ² is an alkali metal in the general formula [I], the general formula [II]

[0018]

[Chemical 7]

(Wherein, X and Y each independently represent a hydrogen atom or a halogen atom, and R ¹ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group.) It is obtained by treating with a hydroxide of an alkali metal such as sodium.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 N- (4'-chloro-2'-fluoro-5'-propal
Giloxyphenyl) -3,4,5,6-tetrahydro
Preparation of phthalamic acid methyl ester (according to synthetic method a) N- (4'-chloro-2'-fluoro-5'-propargyloxyphenyl) -3,4,5,6-tetrahydrophthalamic acid was suspended in 45 ml of ether. It became turbid, and the diazomethane-ether solution was added dropwise at room temperature with stirring. When the solution became almost in solution, the dropping was terminated, the ether was distilled off, and the obtained residue was recrystallized from n-hexane-ethyl acetate to obtain 0.83 g of the desired white crystal.

Melting point 135.5-136.5 ° C. Example 2 N- (4′-chloro-2′-fluoro-5′-methoxy)
Phenyl) -3,4,5,6-tetrahydrophthalamine
Production of acid propargyl ester (according to synthetic method b) N- (4′-chloro-2′-fluoro-5′-methoxyphenyl) -2,2-dichloropropionimidoyl chloride 1.57 g and 3,4,5,5 1.02 g of 6-tetrahydrophthalic acid monopropargyl ester and 0.54 g of triethylamine were dissolved in 15 ml of N, N-dimethylformamide (DMF) and stirred at 60 ° C. for 2.5 hours. After allowing to cool, the reaction solution was poured into ice water to separate the organic layer. The extract was washed with water and saturated saline and then dried over anhydrous magnesium sulfate. The solvent was concentrated, methanol was added to the residue, and the mixture was stirred overnight at room temperature, then concentrated and the residue was mixed with n.
-Hexane-ethyl acetate was added, and the generated crystals were filtered,
It was dried to obtain 0.29 g of the needle crystal, which was the target substance.

Melting point 140-141 ° C. Example 3 N- (4′-chloro-2′-fluoro-5′-methoxy)
Phenyl) -3,4,5,6-tetrahydrophthalamine
Production of lithium acid salt (according to synthetic method c) N- (4'-chloro-2'-fluoro-5'-methoxyphenyl) -3,4,5,6-tetrahydrophthalamic acid 0.60 g in methanol 5 ml A solution prepared by suspending and stirring 0.084 g of lithium hydroxide monohydrate in 5 ml of water was added dropwise while maintaining the reaction temperature of 0 to 5 ° C. The reaction mixture was stirred for 15 minutes at 0 ° C., then warmed to room temperature,
The solvent is removed under reduced pressure and the product is dried to obtain a white solid 0.5 0.5
9 g was obtained.

Melting point: 225 to 230 ° C. (decomposition) The compounds [I] of the present invention obtained according to the above examples are shown in Table 1 together with the melting points, and ¹ H-N of the representative compound is shown.
The MR absorption spectrum values are shown in Table 2, but the compound of the present invention is not limited thereto.

The compound numbers are also applied to the following examples and test examples.

[0025]

[Table 1]

[0026]

[Table 2]

The herbicide of the present invention containing the compound [I] of the present invention as an active ingredient is a variety of weeds that are problematic in the treatment of flooded soil in paddy fields, for example, broad-leaved leaves such as grass weeds such as Nobye, azena, scabbard, and Mizochabe Weeds, snails, has herbicidal activity against weeds such as cyperaceae weeds such as firefly and weeds, and also various foliage treatment of field, and various weeds that are problematic in soil treatment, such as mustard, Aoyu, Chickweed, Shiroza,
Ona fir, Malva morning glory, Yaemgra, Purslane,
Broad-leaved weeds such as velvetleaf, American horngrass, Ebisugusha, Azuki-noshiro, Anodontopus, Polygonum, Violet, etc. It also has herbicidal activity against family weeds, and the herbicide of the present invention is rice,
It shows almost no harmful phytotoxicity against major crops such as wheat, corn, and soybean.

Therefore, the herbicide of the present invention can be used in fields, paddy fields,
It can be used for orchards, meadows, lawns, forests or non-agricultural land. The herbicide of the present invention contains the above-mentioned compound [I] of the present invention as an active ingredient, and uses an agricultural chemical auxiliary generally used in this field, that is, an inert solid carrier, liquid carrier and emulsifying dispersant. Wettable powder,
It can be used in any dosage form such as emulsion, granule, powder and flowable agent. Examples of these inert carriers include talc, clay, bentonite, kaolin, diatomaceous earth, calcium carbonate, wood flour, starch, gum arabic,
Water, alcohol, kerosene, benzene, xylene, n-
Hexane, acetone, dimethylformamide, glycol ether, N-methylpyrrolidone and the like can be mentioned. In addition, auxiliary agents in the formulation, such as spreading agents, diluents, surfactants, solvents and the like can be appropriately added.

When the compound [I] of the present invention is used as a herbicide, it can be appropriately selected according to its method, purpose, time and the condition of weeds generation, but it is usually 0.1 to 300 g per 10 ares as an active ingredient, preferably It is 1 to 100 g.

Further, the herbicide containing the compound [I] of the present invention is mixed with other kinds of herbicides, plant growth regulators, fungicides, insecticides and other agricultural chemicals, fertilizers, soil conditioners and the like. You can also

Next, examples of the herbicide of the present invention will be given.
The compounds, carriers, auxiliaries and proportions used are not limited to the examples. The constituent ratios of the components in this example are parts by weight.

Example 4 (Wettable powder) Compound of Example 1 10 parts Sodium lignin sulfonate 1.5 parts Polyoxyethylene alkylaryl ether 1.5 parts Clay 87 parts Mixing each of these components until uniform The powder was pulverized to obtain a wettable powder.

Example 5 (Granule) Compound of Example 1 7 parts Bentonite 30 parts Sodium alkyl sulphate 2 parts Clay 61 parts These components were mixed until uniform and kneaded.
Granulation was carried out by a usual granulation method to obtain granules.

Next, the herbicidal effect of the compound [I] of the present invention will be described with reference to test examples. Test Example 1 (Flooded Soil Treatment) A pot of 1/15500 are was filled with paddy soil (clay loam soil), and various weed seeds of Novier, broadleaf weed, firefly, tamagaya and konjac were uniformly mixed and sown on the surface layer. , 2 to 3 leaf stage rice seedlings were transplanted to a depth of 2 cm and 3
It was flooded to a depth of cm. Three days later, at the beginning of the generation of Novier, a predetermined amount of a wettable powder dilution of each compound was dropped on the water surface. After that, it was grown in a glass chamber, and 4 weeks after the treatment, herbicidal effect and paddy rice damage were evaluated. The results are shown in Table 3. In addition,
The numerical values in the table show the rice phytotoxicity and herbicidal effect,
Specifically, it is as follows.

5: Complete death 4: Major harm 3: Medium harm 2: Minor harm 1: Minor harm 0: Harmless (normal growth) Test Example 2 (foliar treatment) Rice cultivated by soil cultivation in a pot of 1/15500 are , The edible millet, Japanese radish, Amaranthus communis, and Phellinus linteus were spray treated with a wettable powder diluent of each compound at the seedling stage (2 to 3 leaf stages). Then, the herbicidal effect was evaluated 4 weeks after the growing and treatment in a glass room. The results are shown in Table 4.
It was shown to. The herbicidal effect was evaluated in the same manner as in Test Example 1.

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

The N-phenyltetrahydrophthalamic acid derivative, which is a novel compound of the present invention, has excellent herbicidal activity and can be applied to fields, paddy fields, orchards, pastures, lawns, forests or non-agricultural land. It provides a widely applicable herbicide and is highly safe for crops.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoshi Suzuki 775-23, Hiramatsumoto-cho, Utsunomiya City, Tochigi Prefecture (72) Inventor Matsue Kawamura 2805, Imafuku Nakadai, Kawagoe City, Saitama Prefecture Central Research Laboratory Tokyo Institute (72) Inventor Yumiko Shirakawa 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Tokyo Co., Ltd. (72) Inventor Kaoru Mori 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Tokyo Glass Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the general formula [I]: (In the formula, X and Y each independently represent a hydrogen atom or a halogen atom, R ¹ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group, and R ² represents a lower alkyl group,
It represents a lower alkenyl group, a lower alkynyl group or an alkali metal. ) N-phenyl tetrahydrophthalamic acid derivative shown by these. 2. A compound represented by the general formula [I]: (In the formula, X and Y each independently represent a hydrogen atom or a halogen atom, R ¹ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group, and R ² represents a lower alkyl group,
It represents a lower alkenyl group, a lower alkynyl group or an alkali metal. The N-phenyl tetrahydrophthalamic acid derivative shown by these is contained as an active ingredient.